Urea (multi)-(meth)acrylate (multi)-silane compositions and articles including the same

ABSTRACT

Urea (multi)-(meth)acrylate (multi)-silane precursor compounds, synthesized by reaction of (meth)acrylated materials having isocyanate functionality with aminosilane compounds, either neat or in a solvent, and optionally with a catalyst, such as a tin compound, to accelerate the reaction. Also described are articles including a substrate, a base (co)polymer layer on a major surface of the substrate, an oxide layer on the base (co)polymer layer; and a protective (co)polymer layer on the oxide layer, the protective (co)polymer layer including the reaction product of at least one urea (multi)-(meth)acrylate (multi)-silane precursor compound synthesized by reaction of (meth)acrylated materials having isocyanate functionality with aminosilane compounds. The substrate may be a (co)polymer film or an electronic device such as an organic light emitting device, electrophoretic light emitting device, liquid crystal display, thin film transistor, or combination thereof. Methods of making the urea (multi)-(meth)acrylate (multi)-silanes and their use in composite films and electronic devices are described.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No. 15/955,151, filed Apr. 17, 2018, now allowed, which is a Continuation of Ser. No.14/419,303, filed Feb. 3, 2015, which is a US 371 Application based onPCT/US2013/028503, filed on Mar. 1, 2013, which claims the benefit ofU.S. Provisional Application Nos. 61/681,003; 61/681,008; 61/681,023;61/681,051; and 61/680,995, all filed on Aug. 8, 2012, the disclosuresof which are incorporated by reference in their entirety herein.

FIELD

The present disclosure relates to the preparation of urea(multi)-(meth)acrylate (multi)-silane compounds and their use inpreparing composite barrier assemblies. More particularly, thedisclosure relates to vapor-deposited protective (co)polymer layersincluding the reaction product of at least one urea(multi)-(meth)acrylate (multi)-silane precursor compound, used inmultilayer composite barrier assemblies in articles and barrier films.

BACKGROUND

Inorganic or hybrid inorganic/organic layers have been used in thinfilms for electrical, packaging and decorative applications. Theselayers can provide desired properties such as mechanical strength,thermal resistance, chemical resistance, abrasion resistance, moisturebarriers, and oxygen barriers. Highly transparent multilayer barriercoatings have also been developed to protect sensitive materials fromdamage due to water vapor. The moisture sensitive materials can beelectronic components such as organic, inorganic, and hybrid organic/inorganic semiconductor devices. The multilayer barrier coatings can bedeposited directly on the moisture sensitive material, or can bedeposited on a flexible transparent substrate such as a (co)polymerfilm.

Multilayer barrier coatings can be prepared by a variety of productionmethods. These methods include liquid coating techniques such assolution coating, roll coating, dip coating, spray coating, spincoating; and dry coating techniques such as Chemical Vapor Deposition(CVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), sputtering andvacuum processes for thermal evaporation of solid materials. Oneapproach for multilayer barrier coatings has been to produce multilayeroxide coatings, such as aluminum oxide or silicon oxide, interspersedwith thin (co)polymer film protective layers. Each oxide/(co)polymerfilm pair is often referred to as a “dyad”, and the alternatingoxide/(co)polymer multilayer construction can contain several dyads toprovide adequate protection from moisture and oxygen. Examples of suchtransparent multilayer barrier coatings and processes can be found, forexample, in U.S. Pat. Nos. 5,440,446 (Shaw et al.); 5,877,895 (Shaw etal.); 6,010,751 (Shaw et al.); 7,018,713 (Padiyath et al.); and6,413,645 (Graff et al.).

SUMMARY

In one aspect, the present disclosure describes compositions of matterincluding at least one urea (multi)-(meth)acrylate (multi)-silanecompound of the formula R_(S)—N(R⁵)—C(O)—N(H)—R_(A). R_(S) is a silanecontaining group of the formula —R¹—[Si(Y_(p))(R²)_(3-p)]_(q), whereinR¹ is a multivalent alkylene, arylene, alkarylene, or aralkylene group,said alkylene, arylene, alkarylene, or aralkylene groups optionallycontaining one or more catenary oxygen atoms, each Y is a hydrolysablegroup, R² is a monovalent alkyl or aryl group; p is 1, 2, or 3, and q is1-5. Additionally, R_(A) is a (meth)acryl group containing group of theformula R¹¹-(A)_(n), in which R¹¹ is a polyvalent alkylene, arylene,alkarylene, or aralkylene group, said alkylene, arylene, alkarylene, oraralkylene groups optionally containing one or more catenary oxygenatoms, A is a (meth)acryl group having the formula X₂—C(O)—C(R³)═CH₂,wherein X² is —O, —S, or —NR³, R³ is H, or C₁-C₄, and n=1 to 5. R⁵ is H,C₁ to C₆ alkyl or cycloalkyl, or R_(S), with the proviso that at leastone of the following conditions applies: n is 2 to 5, R⁵ is R_(S), or qis 2 to 5.

In any of the foregoing embodiments, each hydrolysable group Y isindependently selected from an alkoxy group, an acetate group, anaryloxy group, and a halogen. In some particular exemplary embodimentsof the foregoing, at least some of the hydrolysable groups Y arechlorine.

In another aspect, the present disclosure describes an article includinga substrate selected from a (co)polymeric film or an electronic device,the electronic device further including an organic light emitting device(OLED), an electrophoretic light emitting device, a liquid crystaldisplay, a thin film transistor, a photovoltaic device, or a combinationthereof; an oxide layer on the base (co)polymer layer; and a protective(co)polymer layer on the oxide layer, wherein the protective (co)polymerlayer comprises the reaction product of at least one of the foregoingurea (multi)-(meth)acrylate (multi)-silane precursor compounds of theformula R_(S)—N(R⁵)—C(O)—N(H)—R_(A), as described above.

In yet another aspect, the present disclosure describes an articleincluding a substrate selected from a (co)polymeric film or anelectronic device, the electronic device further including an organiclight emitting device (OLED), an electrophoretic light emitting device,a liquid crystal display, a thin film transistor, a photovoltaic device,or a combination thereof; a base (co)polymer layer on a major surface ofthe substrate, an oxide layer on the base (co)polymer layer; and aprotective (co)polymer layer on the oxide layer, wherein the protective(co)polymer layer includes the reaction product of at least one of theforegoing urea (multi)-(meth)acrylate (multi)-silane precursor compoundsof the formula R_(S1)—N(R⁴)—C(O)—N(H)—R_(A1). R_(S1) is a silanecontaining group of the formula —R^(1d)—Si(Y_(p))(R²)_(3-p), whereinR^(1d) is a divalent alkylene, arylene, alkarylene, or aralkylene group,said alkylene, arylene, alkarylene, or aralkylene groups optionallycontaining one or more catenary oxygen atoms, each Y is a hydrolysablegroup, R² is a monovalent alkyl or aryl group, and p is 1, 2, or 3.Additionally, R⁴ is H, C₁ to C6 alkyl or C₁ to C6 cycloalkyl. RA1 is a(meth)acryl containing group of the formula R^(11d)-(A), wherein R^(11d)is a divalent alkylene, arylene, alkarylene, or aralkylene group, saidalkylene, arylene, alkarylene, or aralkylene groups optionallycontaining one or more catenary oxygen atoms, and A is a (meth)acrylgroup comprising the formula X²—C(O)—C(R³)═CH₂, further wherein X² is—O, —S, or —NR³, and R³ is H, or C₁-C₄.

In any of the foregoing articles, each hydrolysable group Y isindependently selected from an alkoxy group, an acetate group, anaryloxy group, and a halogen. In some particular exemplary embodimentsof the foregoing articles, at least some of the hydrolysable groups Yare chlorine.

In additional exemplary embodiments of any of the foregoing articles,the articles further include a multiplicity of alternating layers of theoxide layer and the protective (co)polymer layer on the base (co)polymerlayer. Some exemplary embodiments of the present disclosure providecomposite barrier assemblies, for example composite barrier films, Thus,in some exemplary embodiments of any of the foregoing articles, thesubstrate includes a flexible transparent (co)polymeric film, optionallywherein the substrate comprises polyethylene terephthalate (PET),polyethylene napthalate (PEN), heat stabilized PET, heat stabilized PEN,polyoxymethylene, polyvinylnaphthalene, polyetheretherketone, afluoro(co)polymer, polycarbonate, polymethylmethacrylate, poly α-methylstyrene, polysulfone, polyphenylene oxide, polyetherimide,polyethersulfone, polyamideimide, polyimide, polyphthalamide, orcombinations thereof. In other exemplary embodiments of any of theforegoing articles, the base (co)polymer layer includes a (meth)acrylatesmoothing layer.

In further exemplary embodiments of any of the foregoing articles, theoxide layer includes at least one oxide, nitride, carbide or boride ofatomic elements selected from Groups IIA, IIIA, IVA, VA, VIA, VIIA, IB,or IIB, metals of Groups IIIB, IVB, or VB, rare-earth metals, or acombination or mixture thereof. In some exemplary embodiments of any ofthe foregoing articles, the articles further include an oxide layerapplied to the protective (co)polymer layer, optionally wherein theoxide layer includes silicon aluminum oxide.

In a further aspect, the disclosure describes methods of using acomposite film as described above in an article selected from aphotovoltaic device, a solid state lighting device, a display device,and combinations thereof. Exemplary solid state lighting devices includesemiconductor light-emitting diodes (SLEDs, more commonly known asLEDs), organic light-emitting diodes (OLEDs), or polymer light-emittingdiodes (PLEDs). Exemplary display devices include liquid crystaldisplays, OLED displays, and quantum dot displays.

In another aspect, the disclosure describes a process including: (a)applying a base (co)polymer layer to a major surface of a substrate, (b)applying an oxide layer on the base (co)polymer layer, and (c)depositing on the oxide layer a protective (co)polymer layer, whereinthe protective (co)polymer layer includes a (co)polymer formed as thereaction product of at least one of the foregoing urea(multi)-(meth)acrylate (multi)-silane precursor compounds of the formulaR_(S)—N(R⁵)—C(O)—N(H)—R_(A) or R_(S1)—N(R⁴)—C(O)—N(H)—R_(A1), aspreviously described. The substrate is selected from a (co)polymericfilm or an electronic device, the electronic device further including anorganic light emitting device (OLED), an electrophoretic light emittingdevice, a liquid crystal display, a thin film transistor, a photovoltaicdevice, or a combination thereof.

In some exemplary embodiments of the process, the at least one urea(multi)-(meth)acrylate (multi)-silane precursor compound undergoes achemical reaction to form the protective (co)polymer layer at least inpart on the oxide layer. Optionally, the chemical reaction is selectedfrom a free radical polymerization reaction, and a hydrolysis reaction.In any of the foregoing processes, each hydrolysable group Y isindependently selected from an alkoxy group, an acetate group, anaryloxy group, and a halogen. In some particular exemplary embodimentsof the foregoing articles, at least some of the hydrolysable groups Yare chlorine.

In some particular exemplary embodiments of any of the foregoingprocesses, step (a) includes (i) evaporating a base (co)polymerprecursor, (ii) condensing the evaporated base (co)polymer precursoronto the substrate, and (iii) curing the evaporated base (co)polymerprecursor to form the base (co)polymer layer. In certain such exemplaryembodiments, the base (co)polymer precursor includes a (meth)acrylatemonomer.

In certain particular exemplary embodiments of any of the foregoingprocesses, step (b) includes depositing an oxide onto the base(co)polymer layer to form the oxide layer. Depositing is achieved usingsputter deposition, reactive sputtering, chemical vapor deposition, or acombination thereof In some particular exemplary embodiments of any ofthe foregoing processes, step (b) includes applying a layer of aninorganic silicon aluminum oxide to the base (co)polymer layer. Infurther exemplary embodiments of any of the foregoing processes, theprocess further includes sequentially repeating steps (b) and (c) toform a multiplicity of alternating layers of the protective (co)polymerlayer and the oxide layer on the base (co)polymer layer.

In additional exemplary embodiments of any of the foregoing processes,step (c) further includes at least one of co-evaporating the at leastone urea (multi)-(meth)acrylate (multi)-silane precursor compound with a(meth)acrylate compound from a liquid mixture, or sequentiallyevaporating the at least one urea (multi)-(meth)acrylate (multi)-silaneprecursor compound and a (meth)acrylate compound from separate liquidsources. Optionally, the liquid mixture includes no more than about 10wt. % of the urea (multi)-(meth)acrylate (multi)-silane precursorcompound. In further exemplary embodiments of such processes, step (c)further includes at least one of co-condensing the urea(multi)-(meth)acrylate (multi)-silane precursor compound with the(meth)acrylate compound onto the oxide layer, or sequentially condensingthe urea (multi)-(meth)acrylate (multi)-silane precursor compound andthe (meth)acrylate compound on the oxide layer.

In further exemplary embodiments of any of the foregoing processes,reacting the urea (multi)-(meth)acrylate (multi)-silane precursorcompound with the (meth)acrylate compound to form a protective(co)polymer layer on the oxide layer occurs at least in part on theoxide layer.

Some exemplary embodiments of the present disclosure provide compositebarrier assemblies, articles or barrier films which exhibit improvedmoisture resistance when used in moisture exposure applications.Exemplary embodiments of the disclosure can enable the formation ofbarrier assemblies, articles or barrier films that exhibit superiormechanical properties such as elasticity and flexibility yet still havelow oxygen or water vapor transmission rates.

Exemplary embodiments of barrier assemblies or barrier films accordingto the present disclosure are preferably transmissive to both visibleand infrared light. Exemplary embodiments of barrier assemblies orbarrier films according to the present disclosure are also typicallyflexible. Exemplary embodiments of barrier assemblies barrier filmsaccording to the present disclosure generally do not exhibitdelamination or curl that can arise from thermal stresses or shrinkagein a multilayer structure. The properties of exemplary embodiments ofbarrier assemblies or barrier films disclosed herein typically aremaintained even after high temperature and humidity aging.

Various aspects and advantages of exemplary embodiments of thedisclosure have been summarized. The above Summary is not intended todescribe each illustrated embodiment or every implementation of thepresent certain exemplary embodiments of the present disclosure. TheDrawings and the Detailed Description that follow more particularlyexemplify certain preferred embodiments using the principles disclosedherein.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are incorporated in and constitute a part ofthis specification and, together with the description, explain theadvantages and principles of exemplary embodiments of the presentdisclosure.

FIG. 1 is a diagram illustrating an exemplary moisture-resistant barrierassembly in an article or film having a vapor-depositedadhesion-promoting coating according to an exemplary embodiment of thepresent disclosure; and

FIG. 2 is a diagram illustrating an exemplary process and apparatus formaking a barrier film according to an exemplary embodiment of thepresent disclosure.

Like reference numerals in the drawings indicate like elements. Thedrawings herein are not drawn to scale, and in the drawings, theillustrated elements are sized to emphasize selected features.

DETAILED DESCRIPTION Glossary

Certain terms are used throughout the description and the claims that,while for the most part are well known, may require some explanation. Itshould understood that, as used herein,

The words “a”, “an”, and “the” are used interchangeably with “at leastone” to mean one or more of the elements being described.

By using words of orientation such as “atop”, “on”, “covering”,“uppermost”, “underlying” and the like for the location of variouselements in the disclosed coated articles, we refer to the relativeposition of an element with respect to a horizontally-disposed,upwardly-facing substrate. It is not intended that the substrate orarticles should have any particular orientation in space during or aftermanufacture.

By using the term “overcoated” to describe the position of a layer withrespect to a substrate or other element of a barrier assembly in anarticle or film of the disclosure, we refer to the layer as being atopthe substrate or other element, but not necessarily contiguous to eitherthe substrate or the other element.

By using the term “separated by” to describe the position of a(co)polymer layer with respect to two inorganic barrier layers, we referto the (co)polymer layer as being between the inorganic barrier layersbut not necessarily contiguous to either inorganic barrier layer.

The terms “barrier assembly,” “barrier film” or “barrier layer” refersto an assembly, film or layer which is designed to be impervious tovapor, gas or aroma migration. Exemplary gases and vapors that may beexcluded include oxygen and/or water vapor.

The term “(meth)acrylate” with respect to a monomer, oligomer orcompound means a vinyl-functional alkyl ester formed as the reactionproduct of an alcohol with an acrylic or a methacrylic acid.

The term “polymer” or “(co)polymer” includes homopolymers andcopolymers, as well as homopolymers or copolymers that may be formed ina miscible blend, e.g., by coextrusion or by reaction, including, e.g.,transesterification. The term “copolymer” includes both random and blockcopolymers.

The term “cure” refers to a process that causes a chemical change, e.g.,a reaction via consumption of water, to solidify a film layer orincrease its viscosity.

The term “cross-linked” (co)polymer refers to a (co)polymer whose(co)polymer chains are joined together by covalent chemical bonds,usually via cross-linking molecules or groups, to form a network(co)polymer. A cross-linked (co)polymer is generally characterized byinsolubility, but may be swellable in the presence of an appropriatesolvent.

The term “cured (co)polymer” includes both cross-linked anduncross-linked (co)polymers.

The term “T_(g)” refer to the glass transition temperature of a cured(co)polymer when evaluated in bulk rather than in a thin film form. Ininstances where a (co)polymer can only be examined in thin film form,the bulk form T_(g) can usually be estimated with reasonable accuracy.Bulk form T_(g) values usually are determined by evaluating the rate ofheat flow vs. temperature using differential scanning calorimetry (DSC)to determine the onset of segmental mobility for the (co)polymer and theinflection point (usually a second-order transition) at which the(co)polymer can be said to change from a glassy to a rubbery state.

Bulk form T_(g) values can also be estimated using a dynamic mechanicalthermal analysis (DMTA) technique, which measures the change in themodulus of the (co)polymer as a function of temperature and frequency ofvibration.

By using the term “visible light-transmissive” support, layer, assemblyor device, we mean that the support, layer, assembly or device has anaverage transmission over the visible portion of the spectrum, T_(vis),of at least about 20%, measured along the normal axis.

The term “metal” includes a pure metal (i.e. a metal in elemental formsuch as, for example silver, gold, platinum, and the like) or a metalalloy.

The term “vapor coating” or “vapor depositing” means applying a coatingto a substrate surface from a vapor phase, for example, by evaporatingand subsequently depositing onto the substrate surface a precursormaterial to the coating or the coating material itself. Exemplary vaporcoating processes include, for example, physical vapor deposition (PVD),chemical vapor deposition (CVD), and combinations thereof.

Various exemplary embodiments of the disclosure will now be describedwith particular reference to the Drawings. Exemplary embodiments of thepresent disclosure may take on various modifications and alterationswithout departing from the spirit and scope of the disclosure.Accordingly, it is to be understood that the embodiments of the presentdisclosure are not to be limited to the following described exemplaryembodiments, but are to be controlled by the limitations set forth inthe claims and any equivalents thereof

Identification of a Problem to be Solved

Flexible barrier assemblies or films are desirable for electronicdevices whose components are sensitive to the ingress of water vapor. Amultilayer barrier assembly or film may provide advantages over glass asit is flexible, light-weight, durable, and enables low cost continuousroll-to-roll processing.

Each of the known methods for producing a multilayer barrier assembly orfilm has limitations. Chemical deposition methods (CVD and PECVD) formvaporized metal alkoxide precursors that undergo a reaction, whenadsorbed on a substrate, to form inorganic coatings. These processes aregenerally limited to low deposition rates (and consequently low linespeeds), and make inefficient use of the alkoxide precursor (much of thealkoxide vapor is not incorporated into the coating). The CVD processalso requires high substrate temperatures, often in the range of300-500° C., which may not be suitable for (co)polymer substrates.

Vacuum processes such as thermal evaporation of solid materials (e.g.,resistive heating or e-beam heating) also provide low metal oxidedeposition rates. Thermal evaporation is difficult to scale up for rollwide web applications requiring very uniform coatings (e.g., opticalcoatings) and can require substrate heating to obtain quality coatings.Additionally, evaporation/sublimation processes can require ion-assist,which is generally limited to small areas, to improve the coatingquality.

Sputtering has also been used to form metal oxide layers. While thedeposition energy of the sputter process used for forming the barrieroxide layer is generally high, the energy involved in depositing the(meth)acrylate layers is generally low. As a result the (meth)acrylatelayer typically does not have good adhesive properties with the layerbelow it, for example, an inorganic barrier oxide sub-layer. To increasethe adhesion level of the protective (meth)acrylate layer to the barrieroxide, a thin sputtered layer of silicon sub-oxide is known to be usefulin the art. If the silicon sub oxide layer is not included in the stack,the protective (meth)acrylate layer has poor initial adhesion to thebarrier oxide. The silicon sub oxide layer sputter process must becarried out with precise power and gas flow settings to maintainadhesion performance. This deposition process has historically beensusceptible to noise resulting in varied and low adhesion of theprotective (meth)acrylate layer. It is therefore desirable to eliminatethe need for a silicon sub oxide layer in the final barrier constructfor increased adhesion robustness and reduction of process complexity.

Even when the “as deposited” adhesion of the standard barrier stack isinitially acceptable, the sub oxide and protective (meth)acrylate layerhas demonstrated weakness when exposed to accelerated aging conditionsof 85° C./85% relative humidity (RH). This inter-layer weakness canresult in premature delamination of the barrier assembly in an articleor film from the devices it is intended to protect. It is desirable thatthe multi-layer construction improves upon and maintains initialadhesion levels when aged in 85° C. and 85%RH.

One solution to this problem is to use what is referred to as a “tie”layer of particular elements such chromium, zirconium, titanium, siliconand the like, which are often sputter deposited as a mono- or thin-layerof the material either as the element or in the presence of small amountof oxygen. The tie layer element can then form chemical bonds to boththe substrate layer, an oxide, and the capping layer, a (co)polymer.

Tie layers are generally used in the vacuum coating industry to achieveadhesion between layers of differing materials. The process used todeposit the layers often requires fine tuning to achieve the right layerconcentration of tie layer atoms. The deposition can be affected byslight variations in the vacuum coating process such as fluctuation invacuum pressure, out-gassing, and cross contamination from otherprocesses resulting in variation of adhesion levels in the product. Inaddition, tie layers often do not retain their initial adhesion levelsafter exposure to water vapor. A more robust solution for adhesionimprovement in a barrier assembly in an article or film is desirable.

Discovery of a Solution to the Problem

We have surprisingly discovered that a composite barrier assembly orfilm comprising a protective (co)polymer layer comprising the reactionproduct of at least one urea (multi)-(meth)acrylate (multi)-silaneprecursor compound as described further below, improves the adhesion andmoisture barrier performance of a multilayer composite barrier assemblyin an article or film. These multilayer composite barrier assemblies orbarrier films have a number of applications in the photovoltaic,display, lighting, and electronic device markets as flexiblereplacements for glass encapsulating materials.

In exemplary embodiments of the present disclosure, the desiredtechnical effects and solution to the technical problem to obtainimproved multilayer composite barrier assemblies or films were obtainedby chemically modifying the compositions used in the process forapplying (e.g., by vapor coating) a protective (co)polymer layer to amultilayer composite barrier assembly in an article or film to achieve,in some exemplary embodiments:

-   -   1) a robust chemical bond with an inorganic oxide surface,    -   2) a robust chemical bond to the (meth)acrylate coating through        (co)polymerization, and    -   3) the maintenance of some of the physical properties of the        modified molecules (e.g., boiling point, vapor pressure, and the        like) such that they can be co-evaporated with a bulk        (meth)acrylate material.

Multilayer Composite Barrier Assemblies or Films

Thus, in exemplary embodiments, the disclosure describes a multilayercomposite barrier assembly in an article or film comprising a substrate,a base (co)polymer layer on a major surface of the substrate, an oxidelayer on the base (co)polymer layer; and a protective (co)polymer layeron the oxide layer, the protective (co)polymer layer comprising thereaction product of at least one urea (multi)-(meth)acrylate(multi)-silane precursor compound having the general formulaR_(A)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(S)]_(n), orR_(S)—NH—C(O)—N(R⁴)—R¹¹—[O—C(O)NH—R_(A)]_(n), as described furtherbelow. The substrate is selected from a (co)polymeric film or anelectronic device, the electronic device further including an organiclight emitting device (OLED), an electrophoretic light emitting device,a liquid crystal display, a thin film transistor, a photovoltaic device,or a combination thereof.

As further explained below, materials of this type may be synthesized byreaction of (meth)acrylated materials having isocyanate functionalitywith aminosilane compounds, either neat or in a solvent, and optionallywith a catalyst, such as a tin compound, to accelerate the reaction.

Turning to the drawings, FIG. 1 is a diagram of an exemplary barrierassembly in an article assembly in an article or film 10 having amoisture resistant coating comprising a single dyad. Barrier assembly inan article or film 10 includes layers arranged in the following order: asubstrate 12; a base (co)polymer layer 14; an oxide layer 16; aprotective (co)polymer layer 18 comprising the reaction product of atleast one urea (multi)-(meth)acrylate (multi)-silane precursor compoundas described herein; and an optional oxide layer 20. Oxide layer 16 andprotective (co)polymer layer 18 together form a dyad and, although onlyone dyad is shown, film 10 can include additional dyads of alternatingoxide layer 16 and protective (co)polymer layer 18 between substrate 10and the uppermost dyad.

In certain exemplary embodiments, the composite barrier assembly in anarticle or film comprises a plurality of alternating layers of the oxidelayer and the protective (co)polymer layer on the base (co)polymerlayer. The oxide layer and protective (co)polymer layer together form a“dyad”, and in one exemplary embodiment, the barrier assembly in anarticle or film can include more than one dyad, forming a multilayerbarrier assembly in an article or film. Each of the oxide layers and/orprotective (co)polymer layers in the multilayer barrier assembly in anarticle or film (i.e. including more than one dyad) can be the same ordifferent. An optional inorganic layer, which preferably is an oxidelayer, can be applied over the plurality of alternating layers or dyads.

In some exemplary embodiments, protective (co)polymer layer 18comprising the reaction product of at least one urea(multi)-(meth)acrylate (multi)-silane precursor compound improves themoisture resistance of film 10 and the peel strength adhesion ofprotective (co)polymer layer 18 to the underlying oxide layer, leadingto improved adhesion and delamination resistance within the furtherbarrier stack layers, as explained further below. Presently preferredmaterials for use in the barrier assembly in an article or film 10 arealso identified further below, and in the Examples.

Protective Polymer Layers

The present disclosure describes protective (co)polymer layers used incomposite barrier assemblies or films (i.e. as barrier films) useful inreducing oxygen and/or water vapor barrier transmission when used aspackaging materials, for example, to package electronic devices. Eachprotective (co)polymer layer includes in its manufacture at least onecomposition of matter described herein as a urea (multi)-(meth)acrylate(multi)-silane precursor compound, the reaction product thereof forms a(co)polymer, as described further below.

Thus, in some exemplary embodiments, the present disclosure describes acomposite barrier assembly or film comprising a substrate, a base(co)polymer layer on a major surface of the substrate, an oxide layer onthe base (co)polymer layer, and a protective (co)polymer layer on theoxide layer, wherein the protective (co)polymer layer comprises thereaction product of at least one of the foregoing urea(multi)-(meth)acrylate (multi)-silane precursor compounds of the formulaR_(S)—N(R⁵)—C(O)—N(H)—R_(A), as described further below.

In other exemplary embodiments, the present disclosure describes acomposite barrier assembly in an article or film including a substrate,a base (co)polymer layer on a major surface of the substrate, an oxidelayer on the base (co)polymer layer, and a protective (co)polymer layeron the oxide layer, wherein the protective (co)polymer layer includesthe reaction product of at least one of the foregoing urea(multi)-(meth)acrylate (multi)-silane precursor compounds of the formulaR_(S1)—N(R⁴)—C(O)—N(H)—R_(A1). R_(S1) is a silane containing group ofthe formula —R^(1d)—Si(Y_(p))(R²)_(3-p), wherein R^(1d) is a divalentalkylene, arylene, alkarylene, or aralkylene group, said alkylene,arylene, alkarylene, or aralkylene groups optionally containing one ormore catenary oxygen atoms, each Y is a hydrolysable group, R² is amonovalent alkyl or aryl group, and p is 1, 2, or 3. Additionally, R⁴ isH, C₁ to C6 alkyl or C₁ to C6 cycloalkyl. RA1 is a (meth)acrylcontaining group of the formula R^(11d)-(A), wherein R^(11d) is adivalent alkylene, arylene, alkarylene, or aralkylene group, saidalkylene, arylene, alkarylene, or aralkylene groups optionallycontaining one or more catenary oxygen atoms, and A is a (meth)acrylgroup comprising the formula X²—C(O)—C(R³)═CH2, further wherein X² is—O, —S, or —NR³, and R³ is H, or C₁-C₄.

In any of the foregoing articles, each hydrolysable group Y isindependently selected from an alkoxy group, an acetate group, anaryloxy group, and a halogen. In some particular exemplary embodimentsof the foregoing articles, at least some of the hydrolysable groups Yare chlorine.

Composite Barrier Assembly or Barrier Film Materials

The present disclosure describes protective (co)polymer layerscomprising the reaction product of at least one urea (multi)-urethane(meth)acrylate-silane precursor compound having the general formulaR_(A)—NH—C(O)—N(R₄)—R¹¹—[O—C(O)NH—R_(S)]_(n), orR_(S)—NH—C(O)—N(R₄)—R¹¹—[O—C(O)NH—R_(A)]_(n), as described furtherbelow. Among other things, (co)polymer layers comprising such reactionproduct(s) of at least one urea (multi)-urethane (meth)acrylate-silaneprecursor compound are useful for improving the interlayer adhesion ofcomposite barrier assembly in an article or films.

Urea (Multi)-(Meth)Acrylate (Multi)-Silane Precursor Compounds

The present disclosure also describes new compositions of mattercomprising at least one urea (multi)-(meth)acrylate (multi)-silanecompound of the formula: R_(S)—N(R⁵)—C(O)—N(H)—R_(A). R_(S) is a silanecontaining group of the formula —R¹—[Si(Y_(p))(R²)_(3-p)]_(q), whereinR¹ is a multivalent alkylene, arylene, alkarylene, or aralkylene group,said alkylene, arylene, alkarylene, or aralkylene groups optionallycontaining one or more catenary oxygen atoms, each Y is a hydrolysablegroup, R² is a monovalent alkyl or aryl group; p is 1, 2, or 3, and q is1-5. Additionally, R_(A) is a (meth)acryl group containing group of theformula R¹¹-(A)_(n), in which R¹¹ is a polyvalent alkylene, arylene,alkarylene, or aralkylene group, said alkylene, arylene, alkarylene, oraralkylene groups optionally containing one or more catenary oxygenatoms, A is a (meth)acryl group having the formula X²—C(O)—C(R³)═CH₂,wherein X² is —O, —S, or —NR³, R³ is H, or C₁-C₄, and n=1 to 5. R⁵ is H,C₁ to C6 alkyl or cycloalkyl, or R_(S), with the proviso that at leastone of the following conditions applies: n is 2 to 5, R⁵ is R_(S), or qis 2 to 5.

In any of the foregoing embodiments, each hydrolysable group Y isindependently selected from an alkoxy group, an acetate group, anaryloxy group, and a halogen. In some particular exemplary embodimentsof the foregoing, at least some of the hydrolysable groups Y arechlorine.

As further explained below, urea (multi)-(meth)acrylate (multi)-silanecompositions may be synthesized by reaction of (meth)acrylated materialshaving isocyanate functionality with aminosilane compounds, either neator in a solvent, and optionally with a catalyst, such as a tin compound,to accelerate the reaction.

Some of these urea (multi)-(meth)acrylate (multi)-silane compositionscontain only one silane group and only one (meth)acryl group, and are ofthe formula:

R_(S1)—N(R⁴)—C(O)—N(H)—R_(A1)  (1)

wherein:R_(S1) is a silane containing group of the formula:

—R^(1d)—Si(Y_(p))(R²)_(3-p) wherein:

R^(1d) is a divalent alkylene, arylene, alkarylene, or aralkylene group,said alkylene, arylene, alkarylene, or aralkylene groups optionallycontaining one or more catenary oxygen atoms,

Y is a hydrolysable group, which includes alkoxy groups, acetate groups,aryloxy groups, and halogens, especially chlorine, and

R² is a monovalent alkyl or aryl group, and

p is 1, 2, or 3;

R_(A1) is a (meth)acryl group containing group of the formula:

R^(11d)-(A) wherein:

R^(11d) is a divalent alkylene, arylene, alkarylene, or aralkylenegroup, said alkylene, arylene, alkarylene, or aralkylene groupsoptionally containing one or more catenary oxygen atoms, and

A is a (meth)acryl group comprising the formula X²—C(O)—C(R³)═CH₂:

-   -   wherein X² is —O, —S, or —NR³, further wherein R³ is H, or        C₁-C₄; and R⁴ is H, C₁ to C6 alkyl or cycloalkyl.

Some of the exemplary urea (multi)-(meth)acrylate (multi)-silanecompositions contain two or more silane groups and/or two or more(meth)acryl groups, and have the general formula:

R_(S)—N(R⁵)—C(O)—N(H)—R_(A)  (2)

wherein:R_(S) is a silane containing group of the formula:

—R¹—[Si(Y_(p))(R²)_(3-p)]_(q)

wherein:

R¹ is a multivalent alkylene, arylene, alkarylene, or aralkylene group,said alkylene, arylene, alkarylene, or aralkylene groups optionallycontaining one or more catenary oxygen atoms,

Y is a hydrolysable group, which includes alkoxy groups, acetate groups,aryloxy groups, and halogens, especially chlorine, and

R² is a monovalent alkyl or aryl group; and

p is 1, 2, or 3,

q is 1-5

R_(A) is a (meth)acryl group containing group of the formula:

R¹¹-(A)_(n) wherein:

R¹¹ is a polyvalent alkylene, arylene, alkarylene, or aralkylene group,said alkylene, arylene, alkarylene, or aralkylene groups optionallycontaining one or more catenary oxygen atoms,

A is a (meth)acryl group comprising the formula X²—C(O)—C(R³)═CH₂wherein:

X² is —O, —S, or —NR³, where R³ is H, or C₁-C₄; and n=1 to 5; and

R⁵ is H, C₁ to C6 alkyl or cycloalkyl, or R_(S), with the proviso thatat least one of the following conditions applies:

n is 2 to 5, R⁵ is R_(S), or q is 2 to 5.

Some suitable (meth)acrylated materials having mono-isocyanatefunctionality include 3-isocyanatoethyl methacrylate, 3-isocyanatoethylmethacrylate, and 1,1-bis(acryloyloxymethyl) ethyl isocyanate.

Aminosilanes suitable for use in connection with the present disclosuremay be primary or secondary. Some primary aminosilanes useful in thepractice of this disclosure are described in U.S. Pat. No. 4,378,250(Treadway et al., incorporated herein by reference in its entirety) andinclude aminoethyltriethoxysilane, β-aminoethyltrimethoxysilane,β-aminoethyltriethoxysilane, β-aminoethyltributoxysilane,β-aminoethyltripropoxysilane, α-amino-ethyltrimethoxysilane,α-aminoethyltriethoxysilane, γ-aminopropyltrimethoxy -silane,γ-aminopropyltriethoxysilane, γ-aminopropyltributoxysilane,γ-aminopropyl-tripropoxysilane, β-aminopropyltrimethoxysilane,β-aminopropyltriethoxysilane, β-amino-propyltripropoxysilane,β-aminopropyltributoxysilane, α-aminopropyltrimethoxysilane,α-aminopropyltriethoxysilane, α-aminopropyltributoxysilane, andα-aminopropyltri-propoxysilane.

Some secondary aminosilanes useful in the practice of the disclosureinclude N-methyl aminopropyltrimethoxysilane, N-methylaminopropyltriethoxysilane, bis(propyl-3-trimethoxysilane) amine,bis(propyl-3-triethoxysilane) amine,N-butyl-aminopropyltrimethoxysilane, N-butyl aminopropyltriethoxysilane,N-cyclohexyl-aminopropyltrimethoxysilane, N-cyclohexylaminomethyltrimethoxysilane, N-cyclohexyl aminomethyltriethoxysilane,and N-cyclohexyl aminomethyldiethoxy-monomethylsilane.

Typical preparation procedures for urea compounds can be found inPolyurethanes: Chemistry and Technology, Saunders and Frisch,Interscience Publishers (New York, 1963 (Part I) and 1964 (Part II).

The molecular weight of the urea (multi)-(meth)acrylate (multi)-silaneprecursor compound is in the range where sufficient vapor pressure atvacuum process conditions is effective to carry out evaporation and thensubsequent condensation to a thin liquid film. The molecular weights arepreferably less than about 2,000 Da, more preferably less than 1,000 Da,even more preferably less than 500 Da.

Preferably, the urea (multi)-(meth)acrylate (multi)-silane precursorcompound is present at no more than 20% by weight (% wt.) of the vaporcoated mixture; more preferably no more than 19%, 18%, 17%, 16%, 15%,14%, 13%, 12%, 11%, and even more preferably 10%, 9%, 8%, 7%, 6%, 5%,4%, 3%, 2% or even 1% wt. of the vapor deposited mixture.

An optional inorganic layer, which preferably is an oxide layer, can beapplied over the protective (co)polymer layer. Presently preferredinorganic layers comprise at least one of silicon aluminum oxide orindium tin oxide.

Substrates

The substrate 12 is selected from a (co)polymeric film or an electronicdevice, the electronic device further including an organic lightemitting device (OLED), an electrophoretic light emitting device, aliquid crystal display, a thin film transistor, a photovoltaic device,or a combination thereof.

Typically, the electronic device substrate is a moisture sensitiveelectronic device. The moisture sensitive electronic device can be, forexample, an organic, inorganic, or hybrid organic/inorganicsemiconductor device including, for example, a photovoltaic device suchas a copper indium gallium (di)selenide (CIGS) solar cell; a displaydevice such as an organic light emitting display (OLED), electrochromicdisplay, electrophoretic display, or a liquid crystal display (LCD) suchas a quantum dot LCD display; an OLED or other electroluminescent solidstate lighting device, or combinations thereof and the like.

In some exemplary embodiments, substrate 12 can be a flexible, visiblelight-transmissive substrate, such as a flexible light transmissive(co)polymeric film. In one presently preferred exemplary embodiment, thesubstrates are substantially transparent, and can have a visible lighttransmission of at least about 50%, 60%, 70%, 80%, 90% or even up toabout 100% at 550 nm.

Exemplary flexible light-transmissive substrates include thermoplasticpolymeric films including, for example, polyesters, polyacrylates (e.g.,polymethyl methacrylate), polycarbonates, polypropylenes, high or lowdensity polyethylenes, polysulfones, polyether sulfones, polyurethanes,polyamides, polyvinyl butyral, polyvinyl chloride, fluoropolymers (e.g.,polyvinylidene difluoride, ethylenetetrafluoroethylene (ETFE)(co)polymers, terafluoroethylene (co)polymers, hexafluoropropylene(co)polymers, polytetrafluoroethylene, and copolymers thereof),polyethylene sulfide, cyclic olefin (co)polymers, and thermoset filmssuch as epoxies, cellulose derivatives, polyimide, polyimide benzoxazoleand polybenzoxazole.

Presently preferred polymeric films comprise polyethylene terephthalate(PET), polyethylene napthalate (PEN), heat stabilized PET, heatstabilized PEN, polyoxymethylene, polyvinylnaphthalene,polyetheretherketone, fluoropolymer, polycarbonate,polymethylmethacrylate, poly α-methyl styrene, polysulfone,polyphenylene oxide, polyetherimide, polyethersulfone, polyamideimide,polyimide, polyphthalamide, or combinations thereof.

In some exemplary embodiments, the substrate can also be a multilayeroptical film (“MOF”), such as those described in U.S. Patent ApplicationPublication No. US 2004/0032658 A1. In one exemplary embodiment, thefilms can be prepared on a substrate including PET.

The substrate may have a variety of thicknesses, e.g., about 0.01 toabout 1 mm. The substrate may however be considerably thicker, forexample, when a self-supporting article is desired. Such articles canconveniently also be made by laminating or otherwise joining a disclosedfilm made using a flexible substrate to a thicker, inflexible or lessflexible supplemental support.

The (co)polymeric film can be heat-stabilized, using heat setting,annealing under tension, or other techniques that will discourageshrinkage up to at least the heat stabilization temperature when the(co)polymeric film is not constrained.

Base (Co)polymer Layer

Returning to FIG. 1, the base (co)polymer layer 14 can include any(co)polymer suitable for deposition in a thin film. In one aspect, forexample, the base (co)polymer layer 14 can be formed from variousprecursors, for example, (meth)acrylate monomers and/or oligomers thatinclude acrylates or methacrylates such as urethane (meth)acrylates,isobornyl (meth)acrylate, dipentaerythritol penta(meth)acrylate, epoxy(meth)acrylates, epoxy (meth)acrylates blended with styrene,di-trimethylolpropane tetra(meth)acrylate, diethylene glycoldi(meth)acrylate, 1,3-butylene glycol di(meth)acrylate,penta(meth)acrylate esters, pentaerythritol tetra(meth)acrylate,pentaerythritol tri(meth)acrylate, ethoxylated (3) trimethylolpropanetri(meth)acrylate, ethoxylated (3) trimethylolpropane tri(meth)acrylate,alkoxylated trifunctional (meth)acrylate esters, dipropylene glycoldi(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated (4)bisphenol a di(metha)crylate, cyclohexane dimethanol di(meth)acrylateesters, isobornyl (meth)acrylate, cyclic di(meth)acrylates, tris(2-hydroxy ethyl) isocyanurate tri(meth)acrylate, and (meth)acrylatecompounds (e.g., oligomers or polymers) formed from the foregoingacrylates and methacrylates. Preferably, the base (co)polymer precursorcomprises a (meth)acrylate monomer.

The base (co)polymer layer 14 can be formed by applying a layer of amonomer or oligomer to the substrate and cross-linking the layer to formthe (co)polymer in situ, e.g., by flash evaporation and vapor depositionof a radiation-cross-linkable monomer, followed by cross-linking using,for example, an electron beam apparatus, UV light source, electricaldischarge apparatus or other suitable device. Coating efficiency can beimproved by cooling the substrate.

The monomer or oligomer can also be applied to the substrate 12 usingconventional coating methods such as roll coating (e.g., gravure rollcoating) or spray coating (e.g., electrostatic spray coating), thencross-linked as set out above. The base (co)polymer layer 14 can also beformed by applying a layer containing an oligomer or (co)polymer insolvent and drying the thus-applied layer to remove the solvent.Chemical Vapor Deposition (CVD) may also be employed in some cases.Preferably, the base (co)polymer layer 14 is formed by flash evaporationand vapor deposition followed by crosslinking in situ, e.g., asdescribed in U.S. Pat. Nos. 4,696,719 (Bischoff), 4,722,515 (Ham),4,842,893 (Yializis et al.), 4,954,371 (Yializis), 5,018,048 (Shaw etal.), 5,032,461(Shaw et al.), 5,097,800 (Shaw et al.), 5,125,138 (Shawet al.), 5,440,446 (Shaw et al.), 5,547,908 (Furuzawa et al.), 6,045,864(Lyons et al.), 6,231,939 (Shaw et al. and 6,214,422 (Yializis); in PCTInternational Publication No. WO 00/26973

(Delta V Technologies, Inc.); in D. G. Shaw and M. G. Langlois, “A NewVapor Deposition Process for Coating Paper and Polymer Webs”, 6thInternational Vacuum Coating Conference (1992); in D. G. Shaw and M. G.Langlois, “A New High Speed Process for Vapor Depositing Acrylate ThinFilms: An Update”, Society of Vacuum Coaters 36th Annual TechnicalConference Proceedings (1993); in D. G. Shaw and M. G. Langlois, “Use ofVapor Deposited Acrylate Coatings to Improve the Barrier Properties ofMetallized Film”, Society of Vacuum Coaters 37th Annual TechnicalConference Proceedings (1994); in D. G. Shaw, M. Roehrig, M. G. Langloisand C. Sheehan, “Use of Evaporated Acrylate Coatings to Smooth theSurface of Polyester and Polypropylene Film Substrates”, RadTech (1996);in J. Affinito, P. Martin, M. Gross, C. Coronado and E. Greenwell,“Vacuum Deposited Polymer/Metal Multilayer Films for OpticalApplication”, Thin Solid Films 270, 43-48 (1995); and in J. D. Affinito,M. E. Gross, C. A. Coronado, G. L. Graff, E. N. Greenwell and P. M.Martin, “Polymer-Oxide Transparent Barrier Layers”, Society of VacuumCoaters 39th Annual Technical Conference Proceedings (1996).

In some exemplary embodiments, the smoothness and continuity of the base(co)polymer layer 14 (and also each oxide layer 16 and protective(co)polymer layer 18) and its adhesion to the underlying substrate orlayer may be enhanced by appropriate pretreatment. Examples of asuitable pretreatment regimen include an electrical discharge in thepresence of a suitable reactive or non-reactive atmosphere (e.g.,plasma, glow discharge, corona discharge, dielectric barrier dischargeor atmospheric pressure discharge); chemical pretreatment or flamepretreatment. These pretreatments help make the surface of theunderlying layer more receptive to formation of the subsequently applied(co)polymeric (or inorganic) layer. Plasma pretreatment can beparticularly useful.

In some exemplary embodiments, a separate adhesion promotion layer whichmay have a different composition than the base (co)polymer layer 14 mayalso be used atop the substrate or an underlying layer to improveadhesion. The adhesion promotion layer can be, for example, a separate(co)polymeric layer or a metal-containing layer such as a layer ofmetal, metal oxide, metal nitride or metal oxynitride. The adhesionpromotion layer may have a thickness of a few nm (e.g., 1 or 2 nm) toabout 50 nm, and can be thicker if desired.

The desired chemical composition and thickness of the base (co)polymerlayer will depend in part on the nature and surface topography of thesubstrate. The thickness preferably is sufficient to provide a smooth,defect-free surface to which the subsequent oxide layer can be applied.For example, the base (co)polymer layer may have a thickness of a few nm(e.g., 2 or 3 nm) to about 5 micrometers, and can be thicker if desired.

In another aspect, the barrier assembly includes a substrate selectedfrom a (co)polymer film and a moisture sensitive device, and the barrierlayers are disposed on or adjacent to the substrate. As describedfurther below, the barrier assembly can be deposited directly on a(co)polymer film substrate, or a substrate that includes a moisturesensitive device, a process often referred to as direct deposition ordirect encapsulation. Exemplary direct deposition processes and barrierassemblies or described in U.S. Pat. Nos. 5,654,084 (Affinito);6,522,067 (Graff et al.); 6,548,912 (Graff et al.); 6,573,652 (Graff etal.); and 6,835,950 (Brown et al.).

In some exemplary embodiments, flexible electronic devices can beencapsulated directly with the methods described herein. For example,the devices can be attached to a flexible carrier substrate, and a maskcan be deposited to protect electrical connections from the inorganiclayer(s), (co)polymer layer(s), or other layer(s)s during theirdeposition. The inorganic layer(s), (co)polymeric layer(s), and otherlayer(s) making up the multilayer barrier assembly can be deposited asdescribed elsewhere in this disclosure, and the mask can then beremoved, exposing the electrical connections.

In one exemplary direct deposition or direct encapsulation embodiment,the moisture sensitive device is a moisture sensitive electronic device.The moisture sensitive electronic device can be, for example, anorganic, inorganic, or hybrid organic/inorganic semiconductor deviceincluding, for example, a photovoltaic device such as a copper indiumgallium (di)selenide (CIGS) solar cell; a display device such as anorganic light emitting display (OLED), electrochromic display,electrophoretic display, or a liquid crystal display (LCD) such as aquantum dot LCD display; an OLED or other electroluminescent solid statelighting device, or combinations thereof and the like.

Examples of suitable processes for making a multilayer barrier assemblyand suitable transparent multilayer barrier coatings can be found, forexample, in U.S. Pat. Nos. 5,440,446 (Shaw et al.); 5,877,895 (Shaw etal.); 6,010,751 (Shaw et al.); and 7,018,713 (Padiyath et al.). In onepresently preferred embodiment, the barrier assembly in an article orfilm can be fabricated by deposition of the various layers onto thesubstrate, in a roll-to-roll vacuum chamber similar to the systemdescribed in U.S. Pat. Nos. 5,440,446 (Shaw et al.) and 7,018,713(Padiyath, et al.).

It is presently preferred that the base polymer layer 14 is formed byflash evaporation and vapor deposition followed by crosslinking in situ,e.g., as described in U.S. Pat. Nos. 4,696,719 (Bischoff), 4,722,515(Ham), 4,842,893 (Yializis et al.), 4,954,371 (Yializis), 5,018,048(Shaw et al.), 5,032,461(Shaw et al.), 5,097,800 (Shaw et al.),5,125,138 (Shaw et al.), 5,440,446 (Shaw et al.), 5,547,908 (Furuzawa etal.), 6,045,864 (Lyons et al.), 6,231,939 (Shaw et al. and 6,214,422(Yializis); and in PCT International Publication No. WO 00/26973 (DeltaV Technologies, Inc.).

Oxide Layers

The improved barrier assembly in an article or film includes at leastone oxide layer 16. The oxide layer preferably comprises at least oneinorganic material. Suitable inorganic materials include oxides,nitrides, carbides or borides of different atomic elements. Presentlypreferred inorganic materials included in the oxide layer compriseoxides, nitrides, carbides or borides of atomic elements from GroupsIIA, IIIA, IVA, VA, VIA, VIIA, IB, or IIB, metals of Groups IIIB, IVB,or VB, rare-earth metals, or combinations thereof In some particularexemplary embodiments, an inorganic layer, more preferably an inorganicoxide layer, may be applied to the uppermost protective (co)polymerlayer. Preferably, the oxide layer comprises silicon aluminum oxide orindium tin oxide.

In some exemplary embodiments, the composition of the oxide layer maychange in the thickness direction of the layer, i.e. a gradientcomposition. In such exemplary embodiments, the oxide layer preferablyincludes at least two inorganic materials, and the ratio of the twoinorganic materials changes throughout the thickness of the oxide layer.The ratio of two inorganic materials refers to the relative proportionsof each of the inorganic materials. The ratio can be, for example, amass ratio, a volume ratio, a concentration ratio, a molar ratio, asurface area ratio, or an atomic ratio.

The resulting gradient oxide layer is an improvement over homogeneous,single component layers. Additional benefits in barrier and opticalproperties can also be realized when combined with thin, vacuumdeposited protective (co)polymer layers. A multilayer gradientinorganic-(co)polymer barrier stack can be made to enhance opticalproperties as well as barrier properties.

The barrier assembly in an article or film can be fabricated bydeposition of the various layers onto the substrate, in a roll-to-rollvacuum chamber similar to the system described in U.S. Pat. Nos.5,440,446 (Shaw et al.) and 7,018,713 (Padiyath, et al.). The depositionof the layers can be in-line, and in a single pass through the system.In some cases, the barrier assembly in an article or film can passthrough the system several times, to form a multilayer barrier assemblyin an article or film having several dyads.

The first and second inorganic materials can be oxides, nitrides,carbides or borides of metal or nonmetal atomic elements, orcombinations of metal or nonmetal atomic elements. By “metal ornonmetal” atomic elements is meant atomic elements selected from theperiodic table Groups IIA, IIIA, IVA, VA, VIA, VIIA, IB, or IIB, metalsof Groups IIIB, IVB, or VB, rare-earth metals, or combinations thereof.Suitable inorganic materials include, for example, metal oxides, metalnitrides, metal carbides, metal oxynitrides, metal oxyborides, andcombinations thereof, e.g., silicon oxides such as silica, aluminumoxides such as alumina, titanium oxides such as titania, indium oxides,tin oxides, indium tin oxide (“ITO”), tantalum oxide, zirconium oxide,niobium oxide, aluminum nitride, silicon nitride, boron nitride,aluminum oxynitride, silicon oxynitride, boron oxynitride, zirconiumoxyboride, titanium oxyboride, and combinations thereof. ITO is anexample of a special class of ceramic materials that can becomeelectrically conducting with the proper selection of the relativeproportions of each elemental constituent. Silicon-aluminum oxide andindium tin oxide are presently preferred inorganic materials forming theoxide layer 16.

For purposes of clarity, the oxide layer 16 described in the followingdiscussion is directed toward a composition of oxides; however, it is tobe understood that the composition can include any of the oxides,nitrides, carbides, borides, oxynitrides, oxyborides and the likedescribed above.

In one embodiment of the oxide layer 16, the first inorganic material issilicon oxide, and the second inorganic material is aluminum oxide. Inthis embodiment, the atomic ratio of silicon to aluminum changesthroughout the thickness of the oxide layer, e.g., there is more siliconthan aluminum near a first surface of the oxide layer, graduallybecoming more aluminum than silicon as the distance from the firstsurface increases. In one embodiment, the atomic ratio of silicon toaluminum can change monotonically as the distance from the first surfaceincreases, i.e., the ratio either increases or decreases as the distancefrom the first surface increases, but the ratio does not both increaseand decrease as the distance from the first surface increases. Inanother embodiment, the ratio does not increase or decreasemonotonically, i.e. the ratio can increase in a first portion, anddecrease in a second portion, as the distance from the first surfaceincreases. In this embodiment, there can be several increases anddecreases in the ratio as the distance from the first surface increases,and the ratio is non-monotonic. A change in the inorganic oxideconcentration from one oxide species to another throughout the thicknessof the oxide layer 16 results in improved barrier performance, asmeasured by water vapor transmission rate.

In addition to improved barrier properties, the gradient composition canbe made to exhibit other unique optical properties while retainingimproved barrier properties. The gradient change in composition of thelayer produces corresponding change in refractive index through thelayer. The materials can be chosen such that the refractive index canchange from high to low, or vice versa. For example, going from a highrefractive index to a low refractive index can allow light traveling inone direction to easily pass through the layer, while light travellingin the opposite direction may be reflected by the layer. The refractiveindex change can be used to design layers to enhance light extractionfrom a light emitting device being protected by the layer. Therefractive index change can instead be used to pass light through thelayer and into a light harvesting device such as a solar cell. Otheroptical constructions, such as band pass filters, can also beincorporated into the layer while retaining improved barrier properties.

In order to promote silane bonding to the oxide surface, it may bedesirable to form hydroxyl silanol (Si—OH) groups on a freshly sputterdeposited silicon dioxide (SiO₂) layer. The amount of water vaporpresent in a multi-process vacuum chamber can be controlled sufficientlyto promote the formation of Si—OH groups in high enough surfaceconcentration to provide increased bonding sites. With residual gasmonitoring and the use of water vapor sources the amount of water vaporin a vacuum chamber can be controlled to ensure adequate generation ofSi—OH groups.

Process for Making Articles Including Barrier Assemblies or BarrierFilms

In other exemplary embodiments, the disclosure describes a process, e.g.for making a barrier film on a (co)polymer film substrate or for makingan article by depositing a multilayer composite barrier assembly on anelectronic device substrate, the process including: (a) applying a base(co)polymer layer to a major surface of a substrate, (b) applying anoxide layer on the base (co)polymer layer, and (c) depositing on theoxide layer a protective (co)polymer layer, wherein the protective(co)polymer layer comprises a (co)polymer formed as the reaction productof at least one of the foregoing urea (multi)-(meth)acrylate(multi)-silane precursor compounds of the formulaR_(S)—N(R⁵)—C(O)—N(H)—R_(A) or R_(S1)—N(R⁴)—C(O)—N(H)—R_(A1), aspreviously described.

In some exemplary embodiments of the process, the at least one urea(multi)-(meth)acrylate (multi)-silane precursor compound undergoes achemical reaction to form the protective (co)polymer layer at least inpart on the oxide layer. Optionally, the chemical reaction is selectedfrom a free radical polymerization reaction, and a hydrolysis reaction.In any of the foregoing articles, each hydrolysable group Y isindependently selected from an alkoxy group, an acetate group, anaryloxy group, and a halogen. In some particular exemplary embodimentsof the foregoing articles, at least some of the hydrolysable groups Yare chlorine.

In other exemplary embodiments, the disclosure describes a process, e.g.for making a barrier film on a (co)polymer film substrate or for makingan article by depositing a multilayer composite barrier assembly on anelectronic device substrate, the process including: (a) vapor depositingand curing a base (co)polymer layer onto a major surface of a(co)polymer film substrate; (a) vapor depositing and curing a base(co)polymer layer onto a major surface of a substrate; (b) vapordepositing an oxide layer on the base (co)polymer layer; and (c) vapordepositing and curing onto the oxide layer a protective (co)polymerlayer, the protective (co)polymer layer comprising a (co)polymer formedas the reaction product of at least one of the foregoing urea(multi)-(meth)acrylate (multi)-silane precursor compounds of the formulaR_(S)—N(R⁵)—C(O)—N(H)—R_(A) or R_(S1)—N(R⁴)—C(O)—N(H)—R_(A1), aspreviously described.

The vapor deposition process is generally limited to compositions thatare pumpable (liquid-phase with an acceptable viscosity); that can beatomized (form small droplets of liquid), flash evaporated (high enoughvapor pressure under vacuum conditions), condensable (vapor pressure,molecular weight), and can be cross-linked in vacuum (molecular weightrange, reactivity, functionality).

FIG. 2 is a diagram of a system 22, illustrating a process for makingbarrier assembly in an article or film 10. System 22 is contained withinan inert environment and includes a chilled drum 24 for receiving andmoving the substrate 12 (FIG. 1), as represented by a film 26, therebyproviding a moving web on which to form the barrier layers. Preferably,an optional nitrogen plasma treatment unit 40 may be used to plasmatreat or prime film 26 in order to improve adhesion of the base(co)polymer layer 14 (FIG. 1) to substrate 12 (FIG. 1). An evaporator 28applies a base (co)polymer precursor, which is cured by curing unit 30to form base (co)polymer layer 14 (FIG. 1) as drum 24 advances the film26 in a direction shown by arrow 25. An oxide sputter unit 32 applies anoxide to form layer 16 (FIG. 1) as drum 24 advances film 26.

For additional alternating oxide layers 16 and protective (co)polymerlayers 18, drum 24 can rotate in a reverse direction opposite arrow 25and then advance film 26 again to apply the additional alternating base(co)polymer and oxide layers, and that sub-process can be repeated foras many alternating layers as desired or needed. Once the base(co)polymer and oxide are complete, drum 24 further advances the film,and evaporator 36 deposits on oxide layer 16, the urea(multi)-(meth)acrylate (multi)-silane compound (as described above),which is reacted or cured to form protective (co)polymer layer 18 (FIG.1). In certain presently preferred embodiments, reacting the urea(multi)-(meth)acrylate (multi)-silane compound to form a protective(co)polymer layer 18 on the oxide layer 16 occurs at least in part onthe oxide layer 16.

Optional evaporator 34 may be used additionally to provide otherco-reactants or co-monomers (e.g. additional protective (co)polymercompounds) which may be useful in forming the protective (co)polymerlayer 18 (FIG. 1). For additional alternating oxide layers 16 andprotective (co)polymer layers 18, drum 24 can rotate in a reversedirection opposite arrow 25 and then advance film 26 again to apply theadditional alternating oxide layers 16 and protective (co)polymer layers18, and that sub-process can be repeated for as many alternating layersor dyads as desired or needed.

The oxide layer 16 can be formed using techniques employed in the filmmetalizing art such as sputtering (e.g., cathode or planar magnetronsputtering), evaporation (e.g., resistive or electron beam evaporation),chemical vapor deposition, plating and the like. In one aspect, theoxide layer 16 is formed using sputtering, e.g., reactive sputtering.Enhanced barrier properties have been observed when the oxide layer isformed by a high energy deposition technique such as sputtering comparedto lower energy techniques such as conventional chemical vapordeposition processes. Without being bound by theory, it is believed thatthe enhanced properties are due to the condensing species arriving atthe substrate with greater kinetic energy as occurs in sputtering,leading to a lower void fraction as a result of compaction.

In some exemplary embodiments, the sputter deposition process can usedual targets powered by an alternating current (AC) power supply in thepresence of a gaseous atmosphere having inert and reactive gasses, forexample argon and oxygen, respectively. The AC power supply alternatesthe polarity to each of the dual targets such that for half of the ACcycle one target is the cathode and the other target is the anode. Onthe next cycle the polarity switches between the dual targets. Thisswitching occurs at a set frequency, for example about 40 kHz, althoughother frequencies can be used. Oxygen that is introduced into theprocess forms oxide layers on both the substrate receiving the inorganiccomposition, and also on the surface of the target. The dielectricoxides can become charged during sputtering, thereby disrupting thesputter deposition process. Polarity switching can neutralize thesurface material being sputtered from the targets, and can provideuniformity and better control of the deposited material.

In further exemplary embodiments, each of the targets used for dual ACsputtering can include a single metal or nonmetal element, or a mixtureof metal and/or nonmetal elements. A first portion of the oxide layerclosest to the moving substrate is deposited using the first set ofsputtering targets. The substrate then moves proximate the second set ofsputtering targets and a second portion of the oxide layer is depositedon top of the first portion using the second set of sputtering targets.The composition of the oxide layer changes in the thickness directionthrough the layer.

In additional exemplary embodiments, the sputter deposition process canuse targets powered by direct current (DC) power supplies in thepresence of a gaseous atmosphere having inert and reactive gasses, forexample argon and oxygen, respectively. The DC power supplies supplypower (e.g. pulsed power) to each cathode target independent of theother power supplies. In this aspect, each individual cathode target andthe corresponding material can be sputtered at differing levels ofpower, providing additional control of composition through the layerthickness. The pulsing aspect of the DC power supplies is similar to thefrequency aspect in AC sputtering, allowing control of high ratesputtering in the presence of reactive gas species such as oxygen.Pulsing DC power supplies allow control of polarity switching, canneutralize the surface material being sputtered from the targets, andcan provide uniformity and better control of the deposited material.

In one particular exemplary embodiment, improved control duringsputtering can be achieved by using a mixture, or atomic composition, ofelements in each target, for example a target may include a mixture ofaluminum and silicon. In another embodiment, the relative proportions ofthe elements in each of the targets can be different, to readily providefor a varying atomic ratio throughout the oxide layer. In oneembodiment, for example, a first set of dual AC sputtering targets mayinclude a 90/10 mixture of silicon and aluminum, and a second set ofdual AC sputtering targets may include a 75/25 mixture of aluminum andsilicon. In this embodiment, a first portion of the oxide layer can bedeposited with the 90%Si/10%Al target, and a second portion can bedeposited with the 75%Al/25%Si target. The resulting oxide layer has agradient composition that changes from about 90% Si to about 25% Si (andconversely from about 10% Al to about 75% Al) through the thickness ofthe oxide layer.

In typical dual AC sputtering, homogeneous oxide layers are formed, andbarrier performance from these homogeneous oxide layers suffer due todefects in the layer at the micro and nano-scale. One cause of thesesmall scale defects is inherently due to the way the oxide grows intograin boundary structures, which then propagate through the thickness ofthe film. Without being bound by theory, it is believed several effectscontribute to the improved barrier properties of the gradientcomposition barriers described herein. One effect can be that greaterdensification of the mixed oxides occurs in the gradient region, and anypaths that water vapor could take through the oxide are blocked by thisdensification. Another effect can be that by varying the composition ofthe oxide materials, grain boundary formation can be disrupted resultingin a microstructure of the film that also varies through the thicknessof the oxide layer. Another effect can be that the concentration of oneoxide gradually decreases as the other oxide concentration increasesthrough the thickness, reducing the probability of forming small-scaledefect sites. The reduction of defect sites can result in a coatinghaving reduced transmission rates of water permeation.

In some exemplary embodiments, exemplary films can be subjected topost-treatments such as heat treatment, ultraviolet (UV) or vacuum UV(VUV) treatment, or plasma treatment. Heat treatment can be conducted bypassing the film through an oven or directly heating the film in thecoating apparatus, e.g., using infrared heaters or heating directly on adrum. Heat treatment may for example be performed at temperatures fromabout 30° C. to about 200° C., about 35° C. to about 150° C., or about40° C. to about 70° C.

Other functional layers or coatings that can be added to the inorganicor hybrid film include an optional layer or layers to make the film morerigid. The uppermost layer of the film is optionally a suitableprotective layer, such as optional inorganic layer 20. If desired, theprotective layer can be applied using conventional coating methods suchas roll coating (e.g., gravure roll coating) or spray coating (e.g.,electrostatic spray coating), then cross-linked using, for example, UVradiation. The protective layer can also be formed by flash evaporation,vapor deposition and cross-linking of a monomer as described above.Volatilizable (meth)acrylate monomers are suitable for use in such aprotective layer. In a specific embodiment, volatilizable (meth)acrylatemonomers are employed.

Methods of Using Barrier Films

In a further aspect, the disclosure describes methods of using a barrierfilm made as described above in an article selected from a solid statelighting device, a display device, and combinations thereof. Exemplarysolid state lighting devices include semiconductor light-emitting diodes(SLEDs, more commonly known as LEDs), organic light-emitting diodes(OLEDs), or polymer light-emitting diodes (PLEDs). Exemplary displaydevices include liquid crystal displays, OLED displays, and quantum dotdisplays.

Exemplary LEDs are described in U.S. Pat. No. 8,129,205. Exemplary OLEDsare described in U.S. Pat. Nos. 8,193,698 and 8,221,176. Exemplary PLEDsare described in U.S. Pat. No. 7,943,062.

Unexpected Results and Advantages

Exemplary barrier assemblies in articles or films of the presentdisclosure have a number of applications and advantages in the display,lighting, and electronic device markets as flexible replacements forglass encapsulating materials. Thus, certain exemplary embodiments ofthe present disclosure provide barrier assemblies in articles or filmswhich exhibit improved moisture resistance when used in moisture barrierapplications. In some exemplary embodiments, the barrier assembly can bedeposited directly on a substrate that includes a moisture sensitivedevice, a process often referred to as direct encapsulation.

The moisture sensitive device can be, for example, an organic,inorganic, or hybrid organic/inorganic semiconductor device including,for example, a photovoltaic device such as a CIGS; a display device suchas an OLED, electrochromic, or an electrophoretic display; an OLED orother electroluminescent solid state lighting device, or others.Flexible electronic devices can be encapsulated directly. For example,the devices can be attached to a flexible carrier substrate, and a maskcan be deposited to protect electrical connections from the oxide layerdeposition. A base (co)polymer layer and the oxide layer can bedeposited as described above, and the mask can then be removed, exposingthe electrical connections.

Exemplary embodiments of the disclosed methods can enable the formationof barrier assemblies in articles or films that exhibit superiormechanical properties such as elasticity and flexibility yet still havelow oxygen or water vapor transmission rates. The barrier assemblieshave at least one inorganic or hybrid organic/oxide layer or can haveadditional inorganic or hybrid organic/oxide layers. In one embodiment,the disclosed barrier assemblies can have inorganic or hybrid layersalternating with organic compound, e.g., (co)polymer layers. In anotherembodiment, the barrier assemblies can include an inorganic or hybridmaterial and an organic compound. Barrier assemblies in an article orfilm formed using the disclosed method can have an oxygen transmissionrate (OTR) less than about 1 cc/m²-day, less than about 0.5 cc/m²-day,or less than about 0.1 cc/m²-day. Barrier assemblies in an article orfilm formed using the disclosed method can have an water vaportransmission rate (WVTR) less than about 10 cc/m²-day, less than about 5cc/m²-day, or less than about 1 cc/m²-day.

Exemplary embodiments of barrier assemblies and more particularlybarrier films according to the present disclosure are preferablytransmissive to both visible and infrared light. The term “transmissiveto visible and infrared light” as used herein can mean having an averagetransmission over the visible and infrared portion of the spectrum of atleast about 75% (in some embodiments at least about 80, 85, 90, 92, 95,97, or 98%) measured along the normal axis. In some embodiments, thevisible and infrared light-transmissive barrier assembly has an averagetransmission over a range of 400 nm to 1400 nm of at least about 75% (insome embodiments at least about 80, 85, 90, 92, 95, 97, or 98%). Visibleand infrared light-transmissive barrier assemblies are those that do notinterfere with absorption of visible and infrared light, for example, byphotovoltaic cells. In some embodiments, the visible and infraredlight-transmissive barrier assembly has an average transmission over arange wavelengths of light that are useful to a photovoltaic cell of atleast about 75% (in some embodiments at least about 80, 85, 90, 92, 95,97, or 98%).

In some exemplary barrier film embodiments, a first and second(co)polymeric film substrate, pressure sensitive adhesive layer, andbarrier assembly can be selected based on refractive index and thicknessto enhance transmission to visible and infrared light.

Exemplary barrier assemblies and barrier films according to the presentdisclosure are typically flexible. The term “flexible” as used hereinrefers to being capable of being formed into a roll. In someembodiments, the term “flexible” refers to being capable of being bentaround a roll core with a radius of curvature of up to 7.6 centimeters(cm) (3 inches), in some embodiments up to 6.4 cm (2.5 inches), 5 cm (2inches), 3.8 cm (1.5 inch), or 2.5 cm (1 inch). In some embodiments, theflexible assembly can be bent around a radius of curvature of at least0.635 cm (¼ inch), 1.3 cm (½ inch) or 1.9 cm (¾ inch).

Exemplary barrier assemblies and barrier films according to the presentdisclosure generally do not exhibit delamination or curl that can arisefrom thermal stresses or shrinkage in a multilayer structure. Herein,curl is measured using a curl gauge described in “Measurement of WebCurl” by Ronald P. Swanson presented in the 2006 AWEB conferenceproceedings (Association of Industrial Metallizers, Coaters andLaminators, Applied Web Handling Conference Proceedings, 2006).According to this method curl can be measured to the resolution of 0.25m⁻¹ curvature. In some embodiments, barrier assemblies and barrier filmsaccording to the present disclosure exhibit curls of up to 7, 6, 5, 4,or 3 m⁻¹. From solid mechanics, the curvature of a beam is known to beproportional to the bending moment applied to it. The magnitude ofbending stress is in turn is known to be proportional to the bendingmoment. From these relations the curl of a sample can be used to comparethe residual stress in relative terms. Barrier assemblies and barrierfilms also typically exhibit high peel adhesion to EVA, and other commonencapsulants for photovoltaics, cured on a substrate. The properties ofthe barrier assemblies and barrier films disclosed herein typically aremaintained even after high temperature and humidity aging.

Exemplary embodiments of the present disclosure have been describedabove and are further illustrated below by way of the followingExamples, which are not to be construed in any way as imposinglimitations upon the scope of the present disclosure. On the contrary,it is to be clearly understood that resort may be had to various otherembodiments, modifications, and equivalents thereof which, after readingthe description herein, may suggest themselves to those skilled in theart without departing from the spirit of the present disclosure and/orthe scope of the appended claims.

EXAMPLES

The following examples are intended to illustrate exemplary embodimentswithin the scope of this disclosure. All parts, percentages, and ratiosin the examples are by weight, unless noted otherwise. Notwithstandingthat the numerical ranges and parameters setting forth the broad scopeof the disclosure are approximations, the numerical values set forth inthe specific examples are reported as precisely as possible. Anynumerical value, however, inherently contains certain errors necessarilyresulting from the standard deviation found in their respective testingmeasurements. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques.

Materials

The following materials, abbreviations, and trade names are used in theExamples: 90% Si/10% Al targets were obtained from Materion AdvancedChemicals, Inc., Albuquerque, NM.

ETFE film: Ethylene-tetrafluoroethylene film available from St. GobainPerformance Plastics, Wayne, N.J. under the trade name “NORTON® ETFE.”

Table 1 lists the materials used to prepare (multi) (meth)acrylate(multi) silane compounds according to the foregoing disclosure:

TABLE 1 Materials Used in the Examples Trade Name Material Type orAcronym Description (Meth)acrylated material with BEI1,1-bis(acryloyloxymethyl) ethyl isocyanate functionality isocyanateavailable from CBC America Corp. (Commack, NY) (Meth)acrylated materialwith IEA Isocyanatoethyl (meth)acrylate available isocyanatefunctionality from CBC America Corp. (Commack, NY) (Meth)acrylatedmaterial with IEM Isocyanatoethyl methacrylate available isocyanatefunctionality from CBC America Corp. (Commack, NY) Catalyst DBTDLDibutyltin dilaurate available from Sigma Aldrich, (Milwaukee, WI)Solvent MEK Methyl ethyl ketone available from EMD Chemicals, Inc.Aminosilane Geniosil XL N-cyclohexyl-triethoxysilylmethylamine 926available from Wacker Silicones (Adrian, MI) Aminosilane DynasylanAminopropyltrimethoxysilane available AMMO from Evonik (Piscataway, NJ)Aminosilane Dynasylan Aminopropyltriethoxysilane available AMEO fromEvonik (Piscataway, NJ) Aminosilane Dynasylanbis(3-trimethoxysilylpropyl)amine 1124 available from Evonik(Piscataway, NJ) Aminosilane Dynasylan bis(3-triethoxysilylpropyl)amine1122 available from Evonik (Piscataway, NJ) Aminosilane DynasylanN-(n-butyl)-3- 1189 aminopropyltrimethoxysilane available from Evonik(Piscataway, NJ) Aminosilane — N-methyl-3- aminopropyltrimethoxysilaneavailable from SynQuest Labs (Alachua, FL) Cyclic Azasilane Cyclic AZAN-n-butyl-aza-2,2- Silane 1932.4 dimethoxysilacylopentane available fromGelest, Inc. (Morrisville, PA)

Solvents and other reagents used were obtained from Sigma-AldrichChemical Company (Milwaukee, Wis), unless otherwise specified.

Synthesis of Urea (multi)-(Meth)acrylate (multi)-Silane PrecursorCompounds

Preparatory Example 1

A 250 mL roundbottom flask with a stirbar was charged with 40 g (0.117mol, 341.55 MW) bis(3-trimethoxysilylpropylamine (Dynasylan 1124) andplaced in an ice bath. Via a pressure equalizing addition funnel, 18.17g (0.117 mol) isocyanatoethyl methacrylate (IEM) was added over about 25min. The ice bath was removed and stirring continued for another hourand 15 min. At that point a sample was taken for Fourier TransformInfrared

(FTIR) spectroscopic analysis, with the sample showing no isocyanatepeak at 2265 cm⁻¹. The product, a clear oil, was then isolated:

Preparatory Example 2

A 500 mL roundbottom flask equipped with overhead stirrer was chargedwith 58.50 g (0.414 mol) of isocyanatoethyl (meth)acrylate (IEA) in aroom temperature water bath under dry air. Via a dropping funnel, 141.53g (0.414 mol) of bis(3-trimethoxysilyl-propyl)amine (Dynasylan 1124) wasadded over 1.5 hours. At that point a sample was taken for FTIR, withthe sample showing no isocyanate peak at 2265 cm⁻¹. The substance wascharacterized by Proton Fourier Transform Nuclear Magnetic Resonance(NMR):

Preparatory Example 3

A 250 mL three necked roundbottom flask equipped with an overheadstirrer was charged with 12.36 g (0.0517 mol, 239.23 MW)1,1-bis(acryloyloxymethyl) ethyl isocyanate (BEI), and 176 microlitersof a 10% solution of DBTDL in MEK (500 ppm based on the total weight ofreactants). The flask was placed in a 35° C. oil bath, and 17.64 g(0.517 mol, 341.55 MW) bis-(3-trimethoxysilylpropyl) amine (Dynasylan1124) was added to the reaction via dropping funnel over 1 hour. About10 min after the amine addition was complete, a sample was taken forFTIR, with the sample showing no isocyanate peak at 2265 cm⁻¹. Theproduct, a clear oil, was then isolated:

Preparatory Example 4

An experiment was run similar to Preparatory Example 3, except that12.85 g (0.72 mol, 179.29 MW) aminopropyltrimethoxysilane (DynasylanAMMO) was reacted with 17.15 g (0.72 mol) 1,1-bis(acryloyloxymethyl)ethyl isocyanate (BEI), and 176 microliters of a 10% solution of DBTDLin MEK (500 ppm DBTDL) over about 45 min to provide a the product as anoil:

Preparatory Example 5

An experiment was run similar to Preparatory Example 1, except that22.53 g (0.0529 mol, 425.71 MW) bis(3-triethoxysilylpropylamine(Dynasylan 1122) was reacted with 7.47 g (0.0529 mol) IEA in thepresence of 35 microliters of a 10% solution of DBTDL in MEK (100 ppmDBTDL) to provide the product:

Preparatory Example 6

An experiment was run similar to Preparatory Example 1, except that14.42 g (0.065 mol) of aminopropyltriethoxysilane (Dynasylan AMMO) wasreacted with 15.58 g (0.065 mol) of BEI in the presence of 176microliters of a 10% solution of DBTDL in MEK (500 ppm DBTDL) to providethe product:

Preparatory Example 7

A 200 mL flask equipped with an overhead stirrer was charged with 20.0 g(0.0836 mol) 1,1-bis(acryloyloxymethyl) ethyl isocyanate (BEI) and 250microliters of 10% DBTDL and placed under dry air in a 55° C. oil bath.Then 23.02 g (0.0836 mol) of N-cyclohexyl-triethoxysilylmethylamine(Geniosil XL 926) was added via a dropping funnel over 20 min. Themixture was allowed to react for 1 hour. The product, a clear yellowoil, was then isolated, as shown below. A sample was taken for FTIR,with the sample showing no isocyanate peak at 2265 cm⁻¹.

Preparatory Example 8

A 250mL roundbottom with stirbar was charged with 40 g (0.223 mol,179.29 MW) aminopropyltrimethoxysilane (Dynasylan AMMO) and placed in anice bath. Via a pressure equalizing addition funnel, 34.61 g (0.223 mol,155.15 MW) isocyanatoethyl methacrylate (IEM) was added over about 25min. The ice bath was removed and stirring continued for another hourand 15 min, at which time a sample was taken for FTIR showing noisocyanate peak at 2265 cm⁻¹, and the product, a clear oil, wasisolated:

Preparatory Example 9

In a fashion similar to the preparation of Preparatory Example 8, 40 g(0.170 mol, 235.4 MW) N-(n-butyl)-3-aminopropyltrimethoxysilane(Dynasylan 1189) was reacted with 26.36 g (0.170 mol) IEM to provide theproduct as a clear oil:

Preparatory Example 10

In a fashion similar to the preparation of Preparatory Example 8, 44.10g (0.199 mol, 221.37 MW) aminopropyltriethoxysilane (Dynasylan AMEO) wasreacted with 30.90 g (0.199 mol) IEM to provide the product as a clearoil (Material would solidify at ice bath temperatures):

Preparatory Example 11

In a fashion similar to the preparation of Preparatory Example 8, 41.61g (0.215 mol, 221.37 MW) N-methyl-aminopropyl trimethoxysilane wasreacted with 33.39 g (0.215 mol) IEM to provide the product as a clearoil:

Preparatory Example 12

In a fashion similar to the preparation of Preparatory Example 8, 16.79g (0.0936 mol, 179.29 MW) aminopropyltrimethoxysilane was reacted with13.21 g (0.0936 mol, 141.13 MW) isocyanatoethyl meth)acrylate to (UEA)to provide the urea product:

Preparatory Example 13

In a fashion similar to the preparation of Preparatory Example 8, 18.76g (0.080 mol, 235.4 MW) N-(n-butyl)-3-aminopropyltrimethoxysilane(Dynasylan 1189) was reacted with 11.25 g (0.080 mol) IEA to provide theproduct:

Preparatory Example 14

In a fashion similar to the preparation of Preparatory Example 8, 18.32g (0.0827 mol) aminopropyltriethoxysilane was reacted with 11.68 g(0.0827 mol) IEA to provide the product:

Preparatory Example 15

In a fashion similar to the preparation of Preparatory Example 8, 17.30g (0.090 mol) N-methyl-aminopropyltrimethoxysilane was reacted with12.70 g (0.090 mol) IEA to provide the product:

Preparatory Example 16

A 100 mL roundbottom was charged with 10.16 g (0.072 mol) IEA, and 35microliters of 10% DBTDL in MEK (100ppm DBTDL). Via addition funnel wasadded 19.84 g (0.072 mol, 275.46 MW)N-cyclohexyl-triethoxysilylmethylamine at 55 C over 10 min. After 0.5hrs of further reaction, FTIR analysis showed no isocyanate peak and theproduct was isolated:

Preparatory Example 17

In a fashion similar to the preparation of Preparatory Example 16, 10.81g (0.069 mol) IEM was reacted at 55° C. in the presence of 100 ppm DBTDLwith 19.19 g (0.069 mol) N-cyclohexyl-triethoxysilylmethylamine toprovide the product:

Composite Barrier Assembly and Barrier Film Preparation

Examples of multilayer composite barrier assemblies and barrier filmswere made on a vacuum coater similar to the coater described in U.S.Pat. Nos. 5,440,446 (Shaw et al.) and 7,018,713 (Padiyath, et al.).

Comparative Example 18 and 25 and Examples 19 through 24 below relate toforming simulated display or lighting device packaging modules whichwere subjected to testing under conditions designed to simulate aging inan outdoor environment and then subjected to a peel adhesion test todetermine if the urea (multi)-(meth)acrylate (multi)-silanes of theabove examples were effective in improving peel adhesion. Someprocedures common to all these Examples are presented first.

Multilayer composite barrier assemblies in barrier films according tothe examples below were laminated to a 0.05 mm thick ethylenetetrafluoroethylene (ETFE) film commercially available as NORTON® ETFEfrom St. Gobain Performance Plastics of Wayne, N.J., using a 0.05 mmthick pressure sensitive adhesive (PSA) commercially available as 3MOPTICALLY CLEAR ADHESIVE 8172P from 3M Company, of St. Paul, Minn. Thelaminated barrier sheets formed in each Example below was then placedatop a 0.14 mm thick polytetrafluoroethylene (PTFE) coated aluminum-foilcommercially available commercially as 8656K61, from McMaster-Carr,Santa Fe Springs, Calif. with 13 mm wide desiccated edge tapecommercially available as SOLARGAIN Edge Tape SET LP01″ from TrusealTechnologies Inc. of Solon, Ohio) placed around the perimeter of thefoil between the barrier sheet and the PTFE.

A 0.38 mm thick encapsulant film commercially available as JURASOL fromJuraFilms of Downer Grove, Ill. and an additional layer of the laminatedbarrier sheet were placed on the backside of the foil with theencapsulant between the barrier sheet and the foil. The multi-componentconstructions were vacuum laminated at 150° C. for 12 min.

Test Methods

Aging Test

Some of the laminated constructions described above were aged for 250hrs, 500 hours, and in some cases, 1,000 hours in an environmentalchamber set to conditions of 85° C. and 85% relative humidity (RH).

T-Peel Adhesion Test

Unaged and aged barrier sheets were cut away from the PTFE surface anddivided into 1.0 in wide strips for adhesion testing using the ASTMD1876-08 T-peel test method. The samples were peeled by a peel tester(commercially available under the trade designation “INISIGHT 2 SL” withTestworks 4 software from MTS, Eden Prarie, Minn.) with a 10 in/min(25.4 cm/min) peel rate. The reported adhesion value in Newtons percentimeter (N/cm) is the average of four peel measurements from 1.27 cmto 15.1 cm. The barrier sheets were measured for t-peel adhesion after250 hours of 85° C. and 85% relative humidity and again after 500 and/or1000 hours of exposure.

Example 18 (Comparative)

This example is comparative in the sense that no coupling agents asdescribed in Examples 1 through 17 were used. A polyethyleneterephthalate (PET) substrate film was covered with a stack of a(meth)acrylate smoothing layer, an inorganic silicon aluminum oxide(SiAlOx) barrier and an (meth)acrylate protective layer. The individuallayers were formed as follows:

(Deposition of the (Meth)acrylate Smoothing Layer)

A 305 meter long roll of 0.127 mm thick by 366 mm wide PET filmcommercially available XST 6642 from DuPont of Wilmington, DE was loadedinto a roll-to-roll vacuum processing chamber. The chamber was pumpeddown to a pressure of 1×10⁻⁵ Torr. The web speed was maintained at 4.8meter/min while maintaining the backside of the film in contact with acoating drum chilled to −10° C. With the film in contact with the drum,the film surface was treated with a nitrogen plasma at 0.02 kW of plasmapower. The film surface was then coated with tricyclodecane dimethanoldiacrylate commercially available as SR-833S from Sartomer USA, LLC,Exton, Pa.). More specifically, the diacrylate was degassed under vacuumto a pressure of 20 mTorr prior to coating, loaded into a syringe pump,and pumped at a flow rate of 1.33 mL/min through an ultrasonic atomizeroperated at a frequency of 60 kHz into a heated vaporization chambermaintained at 260° C. The resulting monomer vapor stream condensed ontothe film surface and was electron beam cross-linked using amulti-filament electron-beam cure gun operated at 7.0 kV and 4 mA toform a 720 nm (meth)acrylate layer.

(Deposition of the Inorganic Silicon Aluminum Oxide (SiAlOx) Barrier)

Immediately after the (meth)acrylate deposition and with the film stillin contact with the drum, a SiAlOx layer was sputter-deposited atop the(meth)acrylate-coated web surface. Two alternating current (AC) powersupplies were used to control two pairs of cathodes; with each cathodehousing two 90% Si/10% Al targets commercially available from Materionof Albuquerque, N.M. During sputter deposition, the voltage signal fromeach power supply was used as an input for aproportional-integral-differential control loop to maintain apredetermined oxygen flow to each cathode. The AC power suppliessputtered the 90% Si/10% Al targets using 5000 watts of power, with agas mixture containing 450 sccm argon and 63 sccm oxygen at a sputterpressure of 3.5 millitorr. This provided a 30 nm thick SiAlOx layerdeposited atop the (meth)acrylate discussed above.

(Deposition of the (Meth)acrylate Protective Layer)

Immediately after the SiAlOx layer deposition and with the film still incontact with the drum, an (meth)acrylate protective layer second wascoated and cross-linked on the same web generally using the sameconditions as for the deposition of the smoothing layer, but with thefollowing exceptions. The electron beam cross-linking was carried outusing a multi-filament electron-beam cure gun operated at 7 kV and 5 mA.This provided a 720 nm thick (meth)acrylate layer atop Layer 2.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis) of 87%, determined by averagingthe percent transmission T between 400 nm and 700 nm, measured at a 0°angle of incidence. A water vapor transmission rate (WVTR) was measuredin accordance with ASTM F-1249 at 50° C. and 100% relative humidity (RH)using MOCON PERMATRAN-W® Model 700 WVTR testing system commerciallyavailable from MOCON, Inc, Minneapolis, Minn.). The result was below the0.005 g/m²/day lower detection limit rate of the apparatus. Theresulting three layer barrier assembly stack was used to form asimulated solar module construction as discussed in the section ongeneral procedures above. These simulated solar modules were subjectedto accelerated aging according to the aging test, and then the T-peeladhesion was assessed as discussed above. The results of the T-peeladhesion test are presented in Table 2 below.

Example 19

A polyethylene terephthalate (PET) substrate film was covered with astack of an (meth)acrylate smoothing layer, an inorganic siliconaluminum oxide (SiAlOx) barrier and an (meth)acrylate protective layercontaining the disclosure molecules. The individual layers were formedas in Comparative Example 18 except during the formation of theprotective layer, instead of 100% tricyclodecane dimethanol diacrylateSR-833S being used, a mixture of 97% by weight of tricyclodecanedimethanol diacrylate SR-833S and 3% by weight of the compoundsynthesized in Example 2 above was used instead.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis)=87% and a WVTR below the 0.005g/m²/day, both tested as described in Comparative Example 18. Then theresulting three layer stack was used to form a simulated solar moduleconstruction as discussed in the section on general procedures above.These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

Example 20

A polyethylene terephthalate (PET) substrate film was covered with astack of an (meth)acrylate smoothing layer, an inorganic siliconaluminum oxide (SiAlOx) barrier and an (meth)acrylate protective layercontaining the disclosure molecules. The individual layers were formedas in Comparative Example 18 except during the formation of theprotective layer, instead of 100% tricyclodecane dimethanol diacrylateSR-833S being used, a mixture of 97% by weight of tricyclodecanedimethanol diacrylate SR-833S and 3% by weight of the compoundsynthesized in Preparatory Example 3 above was used instead.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis)=87% and a WVTR below 0.005g/m²/day, both tested as described in Comparative Example 18. Then theresulting three layer stack was used to form a simulated solar moduleconstruction as discussed in the section on general procedures above.These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

Example 21

A polyethylene terephthalate (PET) substrate film was covered with astack of an (meth)acrylate smoothing layer, an inorganic siliconaluminum oxide (SiAlOx) barrier and an (meth)acrylate protective layercontaining the disclosure molecules. The individual layers were formedas in Comparative Example 18 except during the formation of theprotective layer, instead of 100% tricyclodecane dimethanol diacrylateSR-833S being used, a mixture of 97% by weight of tricyclodecanedimethanol diacrylate SR-833S and 3% by weight of the compoundsynthesized in Example 4 above was used instead.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis)=87% and a WVTR below 0.005g/m²/day, both tested as described in Comparative Example 18. Then theresulting three layer stack was used to form a simulated solar moduleconstruction as discussed in the section on general procedures above.These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

Example 22

A polyethylene terephthalate (PET) substrate film was covered with astack of an (meth)acrylate smoothing layer, an inorganic siliconaluminum oxide (SiAlOx) barrier and an (meth)acrylate protective layercontaining the disclosure molecules. The individual layers were formedas in Comparative Example 18 except during the formation of theprotective layer, instead of 100% tricyclodecane dimethanol diacrylateSR-833S being used, a mixture of 97% by weight of tricyclodecanedimethanol diacrylate SR-833S and 3% by weight of the compoundsynthesized in Example 12 above was used instead.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis)=87% and a WVTR below 0.005g/m²/day, both tested as described in Comparative Example 18. Then theresulting three layer stack was used to form a simulated solar moduleconstruction as discussed in the section on general procedures above.These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

Example 23

A polyethylene terephthalate (PET) substrate film was covered with astack of an (meth)acrylate smoothing layer, an inorganic siliconaluminum oxide (SiAlOx) barrier and an (meth)acrylate protective layercontaining the disclosure molecules. The individual layers were formedas in Comparative Example 18 except during the formation of theprotective layer, instead of 100% tricyclodecane dimethanol diacrylateSR-833S being used, a mixture of 97% by weight of tricyclodecanedimethanol diacrylate SR-833S and 3% by weight of the compoundsynthesized in Example 13 above was used instead.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis)=87% and a WVTR below 0.005g/m²/day, both tested as described in Comparative Example 18. Then theresulting three layer stack was used to form a simulated solar moduleconstruction as discussed in the section on general procedures above.These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

Example 24

A polyethylene terephthalate (PET) substrate film was covered with astack of an (meth)acrylate smoothing layer, an inorganic siliconaluminum oxide (SiAlOx) barrier and an (meth)acrylate protective layercontaining the disclosure molecules. The individual layers were formedas in Comparative Example 18 except during the formation of theprotective layer, instead of 100% tricyclodecane dimethanol diacrylateSR-833S being used, a mixture of 97% by weight of tricyclodecanedimethanol diacrylate SR-833S and 3% by weight of the compoundsynthesized in Example 15 above was used instead.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis)=87% and a WVTR below 0.005g/m²/day, both tested as described in Comparative Example 18. Then theresulting three layer stack was used to form a simulated solar moduleconstruction as discussed in the section on general procedures above.These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

Example 25 (Comparative)

A polyethylene terephthalate (PET) substrate film was covered with astack of an (meth)acrylate smoothing layer, an inorganic siliconaluminum oxide (SiAlOx) barrier and an (meth)acrylate protective layercontaining the disclosure molecules. The individual layers were formedas in Comparative Example 18 except during the formation of theprotective layer, instead of 100% tricyclodecane dimethanol diacrylateSR-833S being used, a mixture of 97% by weight of tricyclodecanedimethanol diacrylate SR-833S and 3% by weight ofN-n-butyl-aza-2,2-dimethoxysilacyclopentane (commercially available fromGelest, Morrisville, Pa., under the product code 1932.4) was usedinstead.

The resulting three layer stack on the (co)polymeric substrate exhibitedan average spectral transmission T_(vis)=87% and a WVTR below 0.005g/m²/day, both tested as described in Comparative Example 18. Then theresulting three layer stack was used to form a simulated solar moduleconstruction as discussed in the section on general procedures above.These simulated solar modules were subjected to accelerated agingaccording to the aging test, and then the T-peel adhesion was assessedas discussed above. The results of the T-peel adhesion test arepresented in Table 2 below.

TABLE 2 Test Results for Examples 18-25 T-Peel After Aging T-Peel AfterAging 250 Hours 1000 Hours T-Peel Initial @ 85° C./85% RH @ 85° C./85%RH Example (N/cm) (N/cm) (N/cm) 18 0.3 0.2 0.2 (Comparative) 19 10.710.4 11.1 20 10.4 10.1 1.3 21 10.5 10.2 11.7 22 10.3 10.3 11.1 23 10.710.5 3.0 24 10.3 10.5 11.2 25 6.0 10.1 0.4 (Comparative)

While the specification has described in detail certain exemplaryembodiments, it will be appreciated that those skilled in the art, uponattaining an understanding of the foregoing, may readily conceive ofalterations to, variations of, and equivalents to these embodiments.Accordingly, it should be understood that this disclosure is not to beunduly limited to the illustrative embodiments set forth hereinabove.Furthermore, all publications, published patent applications and issuedpatents referenced herein are incorporated by reference in theirentirety to the same extent as if each individual publication or patentwas specifically and individually indicated to be incorporated byreference.

Various exemplary embodiments have been described. These and otherembodiments are within the scope of the following listing of disclosedembodiments and claims.

1-4. (canceled)
 5. A process, comprising: (a) applying a base(co)polymer layer to a major surface of a substrate selected from a(co)polymeric film or an electronic device, the electronic devicefurther comprising an organic light emitting device (OLED), anelectrophoretic light emitting device, a liquid crystal display, a thinfilm transistor, a photovoltaic device, or a combination thereof; (b)applying an oxide layer on the base (co)polymer layer; and (c)depositing on the oxide layer a protective (co)polymer layer, whereinthe protective (co)polymer layer consists of a (co)polymer formed as teareaction product of a mixture of only a (meth)acrylic compound and atleast one urea (multi)-(meth)acrylate (multi)-silane precursor compoundof the formula:R_(S)—N(R⁵)—C(O)—N(H)—R_(A), wherein: R_(S) is a silane containing groupof the formula:R¹—[Si(Y_(p))(R²)_(3-p)]_(q), wherein: R¹ is a multivalent alkylene,arylene, alkarylene, or aralkylene group, said alkylene, arylene,alkarylene, or aralkylene groups optionally containing one or morecatenary oxygen atoms, Y is a hydrolysable group, R² is a monovalentalkyl or aryl group, p is 1, 2, or 3, and q is 1-5; R_(A) is a(meth)acryl group containing group of the formula:R¹¹-(A)_(n), wherein: R¹¹is a polyvalent alkylene, arylene, alkarylene,or aralkylene group, said alkylene, arylene, alkarylene, or aralkylenegroups optionally containing one or more catenary oxygen atoms, A is a(meth)acryl group comprising the formula X²—C(O)—C(R³)═CH₂ wherein: X²is —O, —S, or —NR³, where R³ is H, or C₁-C₄; and n=1 to 5; and R⁵ is H,Cl to C₆ alkyl, C₃ to C₆ cycloalkyl, or R_(S), with the proviso that atleast one of the following conditions applies: n is 2 to 5, R⁵ is R_(S),or q is 2 to 5, optionally wherein the (meth)acrylic compound istricyclodecane dimethanol diacrylate.
 6. A process, comprising: (a)applying a base (co)polymer layer to a major surface of a substrateselected from a (co)polymeric film or an electronic device, theelectronic device further comprising an organic light emitting device(OLED), an electrophoretic light emitting device, a liquid crystaldisplay, a thin film transistor, a photovoltaic device, or a combinationthereof; (b) applying an oxide layer on the base (co)polymer layer; and(c) depositing on the oxide layer a protective (co)polymer layer,wherein the protective (co)polymer layer consists of only a (co)polymerformed as a reaction product of at least one urea (multi)-(meth)acrylate(multi)-silane precursor compound of the formula:R_(S1)—N(R⁴)—C(O)—N(H)—R_(A1), wherein: R_(S1) is a silane containinggroup of the formula:—R^(1d)—Si(Y_(P))(R²)_(3-p) wherein: R^(1d) is a divalent alkylene,arylene, alkarylene, or aralkylene group, said alkylene, arylene,alkarylene, or aralkylene groups optionally containing one or morecatenary oxygen atoms, Y is a hydrolysable group, R² is a monovalentalkyl or aryl group, and p is 1, 2, or 3; R_(A1) is a (meth)acryl groupcontaining group of the formula:R^(11d)-(A) wherein: R^(11d) is a divalent alkylene, arylene,alkarylene, or aralkylene group, said alkylene, arylene, alkarylene, oraralkylene groups optionally containing one or more catenary oxygenatoms, and A is a (meth)acryl group comprising the formulaX²—C(O)—C(R³)═CH₂: wherein X² is —O, —S, or —NR³, further wherein R³ isH, or C₁-C₄; and R^(a) is H, C₁ to C6 alkyl or cycloalkyl.
 7. Theprocess of claim 5, wherein the at least one urea (multi)-(meth)acrylate(multi)-silane precursor compound undergoes a chemical reaction with the(meth)acrylic compound to form the protective (co)polymer layer at leastin part on the oxide layer, optionally wherein the chemical reaction isa free radical polymerization reaction.
 8. The process of claim 5,wherein each hydrolysable group Y is independently selected from analkoxy group, an acetate group, an aryloxy group, and a halogen.
 9. Theprocess of claim 8, wherein at least some of the hydrolysable groups Yare chlorine.
 10. The process of claim 5, wherein step (a) comprises:(i) evaporating at least one (meth)acrylic compound and at least onebase (co)polymer precursor; (ii) condensing the evaporated at least one(meth)acrylic compound and the at least one base (co)polymer precursoronto the substrate; and (iii) curing the evaporated at least one(methacrylic compound and the at least one base (co)polymer precursor toform the base (co)polymer layer.
 11. The process of claim 5, wherein thebase (co)polymer precursor comprises a (meth)acrylate monomer.)
 12. Theprocess of claim 5, wherein step (b) comprises depositing an oxide ontothe base (co)polymer layer to form the oxide layer, wherein depositingis achieved using sputter deposition, reactive sputtering, chemicalvapor deposition, or a combination thereof.
 13. The process of claim 5,wherein step (b) comprises applying a layer of an inorganic siliconaluminum oxide to the base (co)polymer layer.
 14. The process of claim5, further comprising sequentially repeating steps (b) and (c) to form aplurality of alternating layers of the protective (co)polymer layer andthe oxide layer on the base (co)polymer layer.
 15. The process of claim5, wherein step (c) further comprises at least one of co-evaporating theat least one urea (multi)-(meth)acrylate (multi)-silane precursorcompound with the (meth)acrylate compound from a liquid mixture, orsequentially evaporating the at least one urea (multi)-(meth)acrylate(multi)-silane precursor compound and the (meth)acrylate compound fromseparate liquid sources, optionally wherein the liquid mixture comprisesno more than about 10 wt. % of the urea (multi)-(meth)acrylate(multi)-silane precursor compound.
 16. The process of claim 15, whereinstep (c) further comprises at least one of co-condensing the at leastone urea (multi)-(meth)acrylate (multi)-silane precursor compound withthe (meth)acrylate compound onto the oxide layer, or sequentiallycondensing the at least one urea (multi)-(meth)acrylate (multi)-silaneprecursor compound and the (meth)acrylate compound on the oxide layer.17. The process of claim 5, wherein reacting the at least one urea(multi)-(meth)acrylate (multi)-silane precursor compound with the atloast ono (meth)acrylate compound to form a protective (co)polymer layeron the oxide layer occurs at least in part on the oxide layer.